JP6750249B2 - Photosensitive coloring composition and color filter - Google Patents

Description

The present invention relates to a photosensitive coloring composition, and in particular, in a color filter used for a liquid crystal display device or a solid-state image sensor, a highly sensitive photosensitivity useful for forming each color filter segment of red, green, blue, etc., a black matrix, etc. It relates to a coloring composition. The present invention also relates to a color filter formed by using the photosensitive coloring composition.

The color filter is one in which two or more kinds of fine band-shaped (striped) filter segments of different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or a fine filter segment is arranged vertically and horizontally. It consists of the ones arranged in. The filter segments are as small as several microns to several hundreds of microns, and are arranged in a predetermined arrangement for each hue.
Generally, in a color liquid crystal display device, a transparent electrode for driving the liquid crystal is formed on the color filter by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is further formed thereon. There is. In order to obtain sufficient performance of these transparent electrode and alignment film, it is necessary to form them at a high temperature of generally 200° C. or higher, preferably 230° C. or higher.

For this reason, at present, a method called a pigment dispersion method, which uses a pigment having excellent light resistance and heat resistance as a coloring material, is mainly used as a method for manufacturing a color filter.
In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, and then pattern exposure of one filter color is performed. Then, the unexposed portion is removed in the developing process to form a pattern of the first color, and after the treatment such as heating is added as necessary, the same operation is sequentially repeated for all the filter colors to manufacture a color filter. can do.

2. Description of the Related Art In recent years, color liquid crystal display devices have come to form a large market as liquid crystal color televisions, car navigation systems, and laptop computers integrated with liquid crystal display devices. Monitors and televisions for desktop personal computers that take advantage of the features of energy saving and space saving. As well, it is beginning to spread. Although it is attracting attention as a display device that replaces the conventional CRT, the color reproduction characteristics of the liquid crystal display device are currently inferior to those of the CRT.
Therefore, there is an increasing demand for high color reproducibility in color filters in which filter segments of each color are arranged.

Further, in order to improve the contrast, a black matrix is generally arranged between the filter segments of each color of the color filter. However, in recent years, the material for forming the black matrix is environmentally friendly, has low reflection, and is low in cost. From the point of view, instead of the metallic chromium black matrix, a resin black matrix in which a light-shielding dye is dispersed in a resin is drawing attention. However, the resin black matrix has a problem that it has a lower light-shielding property (optical density) than the metallic chromium black matrix.

In order to improve the color reproducibility of the color filter and the light-shielding property of the black matrix, it is necessary to increase the content of the pigment in the photosensitive coloring composition or increase the film thickness. However, in the method of increasing the content of the pigment, problems such as a decrease in sensitivity, deterioration of developability and resolution occur. In the method of increasing the film thickness, the exposure light does not reach the bottom of the film, and the pattern shape becomes defective.
In order to solve such a problem, it is necessary to increase the sensitivity of the photosensitive coloring composition. Generally, (1) the addition of a reactive double bond of the resin, (2) a photopolymerization initiator, Selection or increase of the sensitizer, (3) selection or increase of the monomer, and the like are performed, and examples thereof include Patent Documents 1 and 2.

JP 2001-264530 A JP, 2003-156842, A

However, there is a limit to the sensitivity improvement only by giving a double bond of the resin and selecting a photopolymerization initiator, a sensitizer and a monomer. In particular, when the amount of the photopolymerization initiator is increased, coloring due to a color peculiar to the photopolymerization initiator, reduction in heat resistance, reduction in light transmittance, reduction in resolution, etc. occur. Moreover, when the amount of the monomer is increased, problems such as tacking occur.
Therefore, the present invention is a photosensitive coloring composition having a high pigment content or a high film thickness, and having high sensitivity and excellent linearity, pattern shape, resolution, development resistance, chemical resistance, and the like. The purpose is to provide a color filter using.

The photosensitive coloring composition of the present invention is represented by the following general formula (1) in order to obtain high sensitivity and excellent linearity, pattern shape, resolution, development resistance and chemical resistance. It is characterized by using a photopolymerization initiator.
That is, the photosensitive coloring composition of the present invention contains a photopolymerization initiator (A) represented by the following general formula (1) and contains a resin (B), a photopolymerizable compound (C), and a colorant. It is a photosensitive coloring composition containing (D).

General formula (1)


[In the general formula (1), R ₁ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group. , Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted Represents an arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms. A group or a substituted or unsubstituted aryl group is shown. ]

The present invention also relates to the above-mentioned photosensitive coloring composition, which further contains another photopolymerization initiator (Y).

Further, the present invention is characterized in that the other photopolymerization initiator (Y) contains at least one compound selected from the group consisting of acetophenone compounds, phosphine compounds, and imidazole compounds. It relates to a coloring composition.

The present invention also relates to the above-mentioned photosensitive coloring composition, which further comprises a polyfunctional thiol (F).

Further, the present invention relates to a color filter comprising a transparent substrate and a filter segment or a black matrix formed from the photosensitive coloring composition.

The photosensitive coloring composition of the present invention, by using a specific oxime ester-based compound as a photopolymerization initiator, has a high pigment content, or even if the formed film thickness of each color filter segment and black matrix is high, it is highly sensitive. Further, it is possible to form each color filter segment and black matrix pattern having excellent linearity, pattern shape, resolution, development resistance, and chemical resistance.
Therefore, a high quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

First, the photosensitive coloring composition in the invention will be specifically described.
The photosensitive coloring composition of the present invention contains a photopolymerization initiator (A) represented by the general formula (1) and contains a resin (B), a photopolymerizable compound (C), and a colorant (D). Contains.
The photopolymerization initiator (A) containing the compound represented by the general formula (1) has high sensitivity, and since a coating film having a particularly high residual film rate can be obtained, the photosensitivity is excellent in the production stability of the color filter. A colored composition is obtained. By using the photosensitive coloring composition containing the photopolymerization initiator, it is possible to form a filter segment and a black matrix having excellent linearity, pattern shape, resolution, development resistance and chemical resistance.
In addition, a better pattern shape can be obtained by using other initiators together.

<Photopolymerization initiator (A)>
The photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention is a compound represented by the general formula (1).

General formula (1)

R ₁ is a hydrogen atom, halogen atom, cyano group, nitro group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted Or an unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted It represents an acyl group or a substituted or unsubstituted amino group.

Of these, an alkyl group is preferred from the viewpoint of synthesis and characteristics as a coloring composition.

In the general formula (1), R ₂ and R ₃ are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number. 3 to 20 cyclic alkyl groups or substituted or unsubstituted aryl groups are shown.

Among them, an alkyl group having 3 to 10 carbon atoms or an alkyl group substituted with a cycloalkyl group is preferable from the viewpoint of synthesis and characteristics as a coloring composition.

The hydrogen atom of the substituent in R _{1 to} R ₃ described above may be further substituted with another substituent.

Examples of such a substituent include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, a phenoxy group and an aryl group such as a p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acetyl group such as methoxalyl group, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, phenylsulfanyl group, arylsulfanyl group such as p-tolylsulfanyl group, alkylamino group such as methylamino group and cyclohexylamino group, Dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, alkyl groups such as methyl group, ethyl group, tert-butyl group and dodecyl group, Aryl group such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, furyl group, heterocyclic group such as thienyl group, hydroxy group, carboxy group, formyl group, Mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, dimethylsulfonium Examples thereof include a mil group and a triphenylphenacylphosphonium group.

The most preferable structure of the photopolymerization initiator (A) includes compounds represented by the following formulas (2) and (3).
Formula (2)

Formula (3)

The photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention is an oxime ester photopolymerization initiator. It is considered that the oxime ester-based photopolymerization initiator decomposes the oxime ester moiety by absorbing ultraviolet light to generate an iminyl radical and an alkyloxy radical, and further decomposes the radical of the active species to cause a reaction. However, since the photopolymerization initiator (A) contained in the photosensitive coloring composition of the present invention has the structure represented by the general formula (1), the decomposition efficiency by ultraviolet irradiation is very high, A pattern can be formed with a small exposure amount.
The photopolymerization initiator (A) of the present invention may function with higher sensitivity than conventional initiators, but the following three reasons are considered to be possible, but details are not clear.

The first reason is that since the photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1), it consists of two oxime ester moieties in one molecule, and radical generation It is thought that the ability is high.

The second reason is that the photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1) that has a good ultraviolet absorbing property, and thus the energy of a given energy ray is extremely high. That is, it can be absorbed well. Furthermore, it is conceivable that the obtained energy is efficiently used for the decomposition of the oxime ester moiety, whereby the decomposition by the energy ray irradiation is fast and a large amount of radicals can be instantly generated.

The third reason is that the photopolymerization initiator (A) of the present invention has a structure represented by the general formula (1) in which decomposition of an iminyl radical generated by absorbing ultraviolet rays into a radical of an active species is represented. It is thought that it is very fast, derived from. If the generated iminyl radicals are metastable, the decomposition will be slow and the amount of active radicals produced will be small, but this is greatly affected by the chemical structure of the ultraviolet absorbing portion. Since the photopolymerization initiator (A) of the present invention has the structure represented by the general formula (1), the iminyl radicals generated by the photoirradiation are decomposed very quickly, and a large amount of radicals are produced. It is believed to have brought.
Further, as described above, the photopolymerization initiator (A) of the present invention is thought to suppress recombination because the decomposition of the iminyl radical is extremely fast. When the number of recombination is large, the number of active species generated by the decomposition decreases, so that the function as a radical polymerization initiator deteriorates.

The photopolymerization initiator (A) represented by the general formula (1) is preferably 1 to 50 parts by weight, and particularly preferably 1 to 100 parts by weight of the colorant (D) in the photosensitive coloring composition. It can be used in amounts of up to 30 parts by weight.

<Other photopolymerization initiator (Y)>
In the photosensitive coloring composition of the present invention, it is preferable to use the photopolymerization initiator (A) represented by the general formula (1) in combination with another photopolymerization initiator (Y) to obtain a better pattern shape. It is preferable because it can be obtained.
Other photopolymerization initiators (Y) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-. 2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1- Acetophenone compounds such as butanone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin compounds such as benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic Benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone and other benzophenone compounds, thioxanthone, 2-chlorothioxanthone, 2-methyl Thioxanthone compounds such as thioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)- s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -Piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis (Trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6- Triazine compounds such as triazine and 2,4-trichloromethyl(4′-methoxystyryl)-6-triazine, 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)], O-(acetyl)-N-(1-phenyl-2-oxo-2-(4′-methoxy-naphthyl)ethylidene)hydroxylamine and other oxime ester compounds, bis( Phosphine compounds such as 2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,2′-bis(o-chlorophenyl)-4,5,4′ ,5'-Tetraphenyl-1,2'-biimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis( imidazole compounds such as o-chlorophenyl)-4,4',5,5'-tetra(p-methylphenyl)biimidazole, and quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone , Borate compounds, carbazole compounds, titanocene compounds and the like are used.

Among these, it is more preferable to contain at least one photopolymerization initiator (Y) selected from the group consisting of acetophenone compounds, phosphine compounds, and imidazole compounds.
These other photopolymerization initiators (Y) can be used alone or as a mixture of two or more kinds at an arbitrary ratio as necessary. The other photopolymerization initiator (Y) can be used in an amount of 1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the colorant (D) in the photosensitive coloring composition. ..
Further, it can be used in an amount of 1 to 3000 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (A). In order to obtain a better pattern shape, the amount is preferably 5 to 2000 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (A).

<Sensitizer (E)>
Further, the photosensitive coloring composition of the present invention may contain a sensitizer (E). The content of the sensitizer (E) can be used in an amount of 1 to 200 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (A) in the photosensitive coloring composition.
Examples of the sensitizer (E) include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. , Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonole derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo Examples include porphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives and the like. ..

More specific examples include Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Tadasaburo Ikemori et al., Special Examples of the sensitizer include those described in "Functional material" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region may be contained.
Among the sensitizers (E), examples of the sensitizer capable of particularly suitably sensitizing the compound represented by the general formula (1) include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis. (Dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.
The sensitizer (E) may contain two or more kinds of sensitizers at any ratio.

<Resin (B)>
The resin (B) contained in the photosensitive coloring composition of the present invention is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the whole wavelength region of 400 to 700 nm in the visible light region. The resin (B) includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone or in combination of two or more.

Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin. , Acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene, polybutadiene, polyimide resin and the like.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

Examples of the photosensitive resin include a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group and an amino group, and a (meth)acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group and an epoxy group, and a cinnamon A resin obtained by reacting an acid to introduce a photocrosslinkable group such as a (meth)acryloyl group or a styryl group into the linear polymer is used. In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is treated with a (meth)acrylic compound having a hydroxyl group such as hydroxyalkyl (meth)acrylate. A half-esterified product can also be used.

The resin (B) can be used in an amount of 1 to 400 parts by weight, preferably 1 to 300 parts by weight, based on 100 parts by weight of the colorant (D) in the photosensitive coloring composition.

<Photopolymerizable compound (C)>
The photopolymerizable compound (C) contained in the photosensitive coloring composition of the present invention is a photopolymerizable monomer or oligomer, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth) ) Acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth) ) Acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, methylolated melamine (Meth)acrylic acid esters, epoxy (meth)acrylates, urethane acrylates, and various other acrylic acid and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol triester Examples thereof include vinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile and the like. These may be used alone or in combination of two or more.

The photopolymerizable compound (C) can be used in an amount of 5 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the colorant (D) in the photosensitive coloring composition.

In the photosensitive coloring composition, the ratio [I _a /M] of the weight [I _a ] of the photopolymerization initiator (A) and the weight [M] of the photopolymerizable compound (C) is 0.01 to 3. 00 is preferable, and 0.15-2.00 is more preferable.
Furthermore, when the photosensitive coloring composition contains a sensitizer (E) or another photopolymerization initiator (Y), the photopolymerization initiator (A), the sensitizer (E) and the other photopolymerization The ratio [I _b /M] of the total weight (I _b ) of the initiator (Y) and the weight [M] of the photopolymerizable compound (C) is preferably 0.01 to 3.00, and 0 It is more preferably 0.15 to 2.00.
When [I _a /M] is 0.15 or more, the development resistance is good, and when [I _b /M] is 0.15 or more, the chemical resistance is also good. When [I _a /M] is 2.00 or less and [I _b /M] is 2.00 or less, the pattern shape, linearity and resolution are more excellent.

<Colorant (D)>
As the colorant (D) contained in the photosensitive coloring composition of the present invention, organic or inorganic pigments can be used alone or in combination of two or more. Among the pigments, pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used. Specific examples of organic pigments that can be used in the photosensitive coloring composition of the present invention are shown below by color index numbers.
Further, as the colorant (D), a dye can be contained within a range that does not lower the heat resistance.

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151. , 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208. , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254. 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Among these, azo pigments, diketopyrrolopyrrole dyes, anthraquinone dyes, quinophthalone dyes, isoindoline dyes, perinone dyes, perylene dyes, and benzimidazolone dyes are mentioned from the viewpoint of lightness and coloring power. Specifically, C.I. I. Pigment Red 176, 177, 179, 254, 242 and a naphthol azo pigment represented by the following general formula (4) are preferable.
General formula (4)
[In the general formula (4), A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , -NHCOR ¹² or -SO ₂ NHR ¹³ is represented. R ^{7 to} R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
However, the case where R ⁴ is —NHCOR ¹² and A, R ² , R ³ , R ⁵ , and R ⁶ are hydrogen atoms and R ¹ is a halogen atom is excluded. ]

Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, and more preferably C.I. I. Pigment Blue 15:6. Further, the aluminum phthalocyanine pigments described in JP-A-2004-333817, JP-A-4893859 and the like can also be used, and the invention is not particularly limited thereto.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Green 7, 36 or 58. Further, the zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like can be used, and the present invention is not particularly limited thereto.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 and the like. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Yellow 138, 139, 150, 185, and a quinophthalone compound represented by the following general formula (5).
General formula (5)

[In the general formula (5), X1 to X13 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. It is aryl group, -SO ₃ H group, -COOH group, a metal salt of -SO ₃ H group or a -COOH group, an alkyl ammonium salt of the -SO ₃ H group or a -COOH group, which may have a substituent A good phthalimidomethyl group or a sulfamoyl group which may have a substituent is shown. The adjacent groups of X1 to X4 and/or X10 to X13 together form an aromatic ring which may have a substituent. ]

Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

The alkyl group which may have a substituent includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isoptyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, and an n-octyl group. Group, stearyl group, linear or branched alkyl group such as 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, penzyl group, 4-methylpentyl group, 4-tert-putylbenzyl group, 4-methoxy Examples thereof include alkyl groups having a substituent such as a penzyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

Further, as the alkoxyl group which may have a substituent, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isoptyloxy group, a tert-putyloxy group, a neopentyloxy group, 2, In addition to linear or branched alkoxyl groups such as 3-dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro Examples thereof include an alkoxyl group having a substituent such as a propoxy group and a benzyloxy group.

Examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group and a p- group. Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 And aryl groups having a substituent such as a 5,8-trichloro-2-naphthyl group, anthraquinonyl group, and 2-aminoanthraquinonyl group.

As the acidic _group, -SO 3 H, -COOH, and examples of the monovalent to trivalent metal salt thereof acidic groups, sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts Etc. Examples of the alkylammonium salt of an acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, quaternary alkyls such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salt. Ammonium salts may be mentioned.

The “substituent in the phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N—CH ₂ —) which may have a substituent and the sulfamoyl group (H ₂ NSO ₂ —) which may have a substituent. "Includes the above-mentioned halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, and the like.

Adjacent groups X1 to X4 and/or X10 to X13 in the general formula (5) are united to form an aromatic ring which may have a substituent. The aromatic ring as used herein includes a hydrocarbon aromatic ring and a heteroaromatic ring, examples of the hydrocarbon aromatic ring include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and the like, and a heteroaromatic ring includes pyridine. Examples thereof include ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring, and carbazole ring.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Examples of orange pigments include C.I. I. Pigment Orange 38, 43, 64, 71, or 73 is raised. Among them, from the viewpoint of brightness and coloring power, C.I. I. Pigment Orange 38, 43 and 64 are preferred.

The black photosensitive coloring composition for forming the black matrix includes, for example, carbon black, aniline black, anthraquinone black pigments, perylene black pigments, specifically C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 or the like can be used. A mixture of a red pigment, a blue pigment, and a green pigment can be used in the black photosensitive coloring composition. As the black pigment, carbon black is preferable in terms of price and light-shielding property, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together with the black photosensitive coloring composition.

The inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, titanium black. , Synthetic iron black, metal oxide powder such as titanium oxide and iron tetroxide, metal sulfide powder, metal powder and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing chroma and lightness.

"dye"
The photosensitive coloring composition of the present invention may contain a dye within a range that does not lower the heat resistance.
Examples of the dye include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, methine dyes, diarylmethane dyes, triarylmethane dyes, xanthene dyes, thiazines. Dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, oxazine dyes, perylene dyes, diketopyrrolopyrrole dyes, quinacridone dyes, ansanthrone dyes, isoindolinone Examples thereof include, but are not limited to, a series dye, an isoindoline series dye, an indanthrone series dye, a coumarin series dye, a quinacridone series dye, a pyranthrone series dye, a flavanthrone series dye, and a perinone series dye.

In recent years, it is necessary to increase the content of the colorant in the photosensitive coloring composition in order to improve the color reproduction characteristics of the color filter and reduce the thickness thereof.
The content of the colorant (D) is preferably 20% by weight or more, more preferably 30% by weight, and particularly preferably 35% by weight or more based on 100% by weight of the solid content of the photosensitive coloring composition for a color filter of the present invention. In this case, sufficient color reproducibility can be obtained and the film thickness can be reduced. Further, when the content is preferably 60% by weight or less, more preferably 50% by weight or less, and particularly preferably 45% by weight or less, the content of the resin as a curing material or the photopolymerizable compound becomes appropriate, and a sufficient cured coating is obtained. You can get a membrane.

<Multifunctional thiol (F)>
The photosensitive coloring composition of the present invention may contain a polyfunctional thiol (F). The polyfunctional thiol (F) is a compound having two or more thiol (SH) groups.
By using the polyfunctional thiol (F) together with the above-mentioned photopolymerization initiator (A), in the radical polymerization process after irradiation with light, a thiyl radical is generated, which acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen. The resulting photosensitive coloring composition has high sensitivity. In particular, a polyfunctional aliphatic thiol having an SH group bonded to an aliphatic group such as methylene or ethylene group is preferable.
For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tris Thioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), trimercaptopropionate tris(2-hydroxy) Ethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine and the like. .. These polyfunctional thiols can be used alone or in combination of two or more.

The content of the polyfunctional thiol (F) is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight, based on 100 parts by weight of the colorant (D).
Better development resistance can be obtained by using 0.05 parts by weight or more of a polyfunctional thiol. When a monofunctional thiol having one thiol (SH) group is used, such improvement in development resistance cannot be obtained.

<Ultraviolet absorber (G), polymerization inhibitor (H)>
The photosensitive coloring composition of the present invention may contain an ultraviolet absorber (G) or a polymerization inhibitor (H). By containing the ultraviolet absorber (G) or the polymerization inhibitor (H), the shape and resolution of the pattern can be controlled. Examples of the ultraviolet absorber include 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl). -1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, etc. Hydroxyphenyltriazine type, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, Benzotriazoles such as 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'. , 4,4'-Tetrahydroxybenzophenone and other benzophenones, phenyl salicylates, p-tert-butylphenyl salicylates and other salicylates, ethyl-2-cyano-3,3'-diphenyl acrylates and other cyanoacrylates System, 2,2,6,6-tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, poly[ [6-[(1,1,3,3-Tetrabutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino ] And the like, and these are used alone or in combination. Examples of the polymerization inhibitor include methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, t-butylcatechol and the like. Amine compounds such as hydroquinone derivatives and phenol compounds, phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, 3,7-dioctylphenothiazine, etc., copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. Copper and manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, and other nitroso compounds, and ammonium salts or aluminum salts thereof, and the like. Alternatively, they are mixed and used.

The ultraviolet absorber (G) and the polymerization inhibitor (H) are 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the colorant (D) in the coloring composition. It can be used in quantity.
Better resolution can be obtained by using 0.01 part by weight or more of the ultraviolet absorber (G) or the polymerization inhibitor (H).

<Solvent>
In the photosensitive coloring composition of the present invention, a coloring agent (D) is sufficiently dispersed in a dye carrier such as a resin (B) or a photopolymerizable compound (C), and a dry film is formed on a transparent substrate such as a glass substrate. A solvent may be contained in order to make it easy to form a filter segment or a black matrix by coating so as to have a thickness of 0.2 to 10 μm. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol , 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene. , N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o- Dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono. Ethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate , Diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, di Propylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether , Propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, acetic acid Examples thereof include n-amyl, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid ester, which may be used alone or in combination.
The solvent can be used in an amount of 100 to 10000 parts by weight, preferably 500 to 5000 parts by weight, based on 100 parts by weight of the colorant (D) in the photosensitive coloring composition.

<Other ingredients>

<Storage stabilizer>
The photosensitive coloring composition of the present invention may contain a storage stabilizer. By containing a storage stabilizer, the viscosity of the composition over time can be stabilized. As the storage stabilizer, for example, 2,6-bis(1,1-dimethylethyl)-4-methylphenol, pentaerystyryl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl) is used. Propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine and other hindered phenols, tetraethylphosphine, tri Phenylphosphine, organic phosphine such as tetraphenylphosphine, zinc dimethyldithiophosphate, zinc dipropyldithiophosphate, phosphite such as molybdenum dibutyldithiophosphate, sulfur such as dodecyl sulfide, benzothiophene, benzyltrimethyl chloride, Examples thereof include quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, and these are used alone or in combination.

The storage stabilizer can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the colorant (D) in the coloring composition.
By using the storage stabilizer in an amount of 0.01 part by weight or more, the temporal stability of the photosensitive coloring composition is improved.

The photosensitive coloring composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve the adhesion to the transparent substrate.
Examples of the silane coupling agent include vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, vinyltrimethoxysilane and other vinylsilanes, γ-methacryloxypropyltrimethoxysilane and other (meth)acrylsilanes, β-( 3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxy) Epoxysilanes such as cyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β (Aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ Examples thereof include aminosilanes such as -aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant (D) in the photosensitive coloring composition.

Further, the photosensitive coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.
Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine and the like can be mentioned.

<Production Method of Photosensitive Coloring Composition>
The photosensitive coloring composition of the present invention comprises various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader and an attritor in which a colorant (D) is dispersed in a dye carrier such as a resin (B) and/or a solvent. A pigment dispersion is finely dispersed by using the pigment dispersion to prepare a photopolymerization initiator (A), a resin (B), a photopolymerizable compound (C) and, in some cases, other photopolymerization initiator ( Y), a sensitizer (E), a polyfunctional thiol (F), an ultraviolet absorber (G), a polymerization inhibitor (H), a storage stabilizer, a solvent, and other components can be mixed and stirred for production. Further, the photosensitive coloring composition containing two or more kinds of pigments is prepared by mixing finely dispersed pigment dispersions separately in a dye carrier and/or a solvent, and further adding a photopolymerization initiator (A) or a photopolymerization initiator (A). It can be manufactured by mixing and stirring the polymerizable compound (C) and the like.

When the colorant (D) is dispersed in the resin (B) and/or the solvent, a dispersion aid such as a resin type pigment dispersant, a surfactant and a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in dispersing the pigment and has a large effect of preventing re-aggregation of the pigment after dispersion, the photosensitivity obtained by dispersing the pigment in the resin (B) and/or the solvent using the dispersion aid. When the coloring composition is used, a color filter having excellent transparency can be obtained.
The dispersion aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the colorant (D).

The resin-type pigment dispersant has a pigment-affinity portion having a property of adsorbing to the pigment and a portion compatible with the pigment carrier, and is adsorbed to the pigment to stabilize the dispersion of the pigment in the pigment carrier. It works. Specific examples of the resin-type pigment dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) with polyester having a free carboxyl group, and the like Oily dispersants such as salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, water-soluble polyvinylpyrrolidone, etc. Resins, water-soluble polymer compounds, polyester systems, modified polyacrylate systems, ethylene oxide/propylene oxide addition compounds, phosphoric acid ester systems and the like are used, and these can be used alone or in combination of two or more.

Examples of commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK-. P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS, Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 24000, manufactured by Lubrizol Japan. 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, BASF EFKA-46, 47, 48, 452. , 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540. , 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Azino PA111, PB711, PB821, PB822, PB824 and the like manufactured by Ajinomoto Fine-Techno Inc. Is mentioned.

As the surfactant, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkyl betaines such as alkyldimethylaminoacetic acid betaine and alkyl imidazolines, and these may be used alone or in combination of two or more. It can be mixed and used.

The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment also includes a naphthalene-based or anthraquinone-based pale yellow aromatic polycyclic compound which is not generally called a pigment. Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. Those which are present can be used, and these can be used alone or in combination of two or more kinds.

The photosensitive coloring composition of the present invention can be prepared in the form of a solvent-developing or alkali-developing colored resist material. The colored resist material is obtained by dispersing a colorant (D) in a composition containing an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (A) and a solvent. Is.

The photosensitive coloring composition is a coarse particle of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more and coarse dust and mixed dust by means of centrifugation, sintering filter, membrane filter or the like. Is preferably removed.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention comprises a filter segment or a black matrix formed from the photosensitive coloring composition of the present invention on a transparent substrate, and a general color filter has at least one red filter segment and at least one red filter segment. It comprises one green filter segment and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment and at least one yellow filter segment.

As the transparent substrate, a glass plate of soda lime glass, low-alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate of polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like is used. In addition, a transparent electrode made of indium oxide, tin oxide or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after paneling.
The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

The formation of each color filter segment and the black matrix by the photolithography method is performed by the following method. That is, a photosensitive colored composition prepared as a solvent-developing or alkali-developing colored resist material is applied to a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating to give a dry film thickness of 0. It is applied so as to have a thickness of 2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or in non-contact with the film.

After that, the filter segment and the black matrix can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion and form a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by the development, heating can be applied if necessary. The photolithography method can form the filter segment and the black matrix with higher accuracy than the printing method.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, a defoaming agent or a surfactant can be added to the developing solution.
As a developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid pour) developing method, or the like can be applied.
In order to increase the ultraviolet exposure sensitivity, a film for preventing polymerization inhibition by oxygen by coating and drying the above-mentioned photosensitive coloring composition and then coating and drying a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin. After forming, the film may be exposed to ultraviolet light.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. In the examples and comparative examples, “part” means “part by weight”.

First, prior to the examples, a method for producing the acrylic resin solutions and the pigment dispersions used in the examples and the comparative examples will be described. In addition, the molecular weight of the resin is HLC-8220GPC (manufactured by Tosoh Corporation) as a device, TSK-GEL SUPER HZM-N as a column, which is connected in series, and is used as a solvent. It is a weight average molecular weight.

<Method for producing acrylic resin solution>
[Preparation of acrylic resin solution]
370 parts of cyclohexanone was placed in a reaction vessel and heated to 80° C. while injecting nitrogen gas into the vessel, at the same temperature, 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate, A mixture of 15.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After the completion of dropping, the mixture was further reacted at 80° C. for 3 hours, then, a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 80° C. for 1 hour. A resin solution was obtained.
After cooling to room temperature, about 2 g of the acrylic resin solution was sampled, heated and dried at 180° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized acrylic resin solution so that the nonvolatile content became 20% by weight. Was added. The weight average molecular weight of the obtained acrylic resin was 40,000.

<Method for producing pigment dispersion>
[Preparation of red pigment dispersion]
After stirring and mixing the mixture having the following composition uniformly, the mixture was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 1 mm, and then filtered with a 5 μm filter. A red pigment dispersion P-R was produced.
Diketopyrrolopyrrole pigment (CI Pigment Red 254) 7.02 parts (BASF's "Irgafore Red B-CF")
Anthraquinone pigment (CI Pigment Red 177) 1.38 parts ("Chromophtal red A2B" manufactured by BASF)
Nickel azo complex pigment (CI Pigment Yellow 150) 0.80 parts (Lanxess "E4GN")
2.05 parts of resin type pigment dispersant ("Solspers 20000" manufactured by Nippon Lubrizol Co., Ltd.)
Diketopyrrolopyrrole pigment derivative 2.00 parts

Acrylic resin solution 13.75 parts Cyclohexanone 73.00 parts

[Preparation of green pigment dispersion]
Using the mixture having the following composition, a green pigment dispersion P-G was prepared in the same manner as the red pigment dispersion.
Copper halide phthalocyanine-based pigment (CI Pigment Green 36) 8.46 parts ("Ryonor Green 6YK" manufactured by Toyo Color Co., Ltd.)
Monoazo pigment (CI Pigment Yellow 150) 2.74 parts (Lanxess "E4GN")
2.80 parts of resin type pigment dispersant ("Solvers 20000" manufactured by Lubrizol Japan)
Acrylic resin solution 10.00 parts Cyclohexanone 76.00 parts

[Preparation of blue pigment dispersion]
Using the mixture having the following composition, a blue pigment dispersion P-B was prepared in the same manner as the red pigment dispersion.
ε type copper phthalocyanine pigment (CIPigment Blue15:6) 11.20 parts (BASF product "Heliogen Blue L-6700F")
Resin-type pigment dispersant 4.62 parts ("Solvers 20000" manufactured by Lubrizol Japan)
Acrylic resin solution 1.00 parts Cyclohexanone 83.18 parts

[Preparation of black pigment dispersion]
A black pigment dispersion P-BK was prepared in the same manner as the red pigment dispersion, using a mixture having the following composition.
Carbon black (“MA77” manufactured by Mitsubishi Chemical Co., Ltd.) 11.20 parts Resin type pigment dispersant 3.82 parts (“Solspers 20000” manufactured by Lubrizol Japan)
Acrylic resin solution 4.90 parts Cyclohexanone 80.08 parts

[Examples 1 to 19 and Comparative Examples 1 to 3]
(Preparation of photosensitive coloring composition)
The materials were mixed and stirred at the prescription ratios shown in Tables 1 to 3 and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

[Examples 1 to 19 and Comparative Examples 1 to 3]
(Preparation of photosensitive coloring composition)
The materials were mixed and stirred at the prescription ratios shown in Tables 1 to 3 and filtered through a 1 μm filter to obtain a photosensitive coloring composition of each color.

The abbreviations in Tables 1 to 3 are shown below.
Photopolymerization initiator A1: Compound formula (2) having a structure of the following formula (2)

Photopolymerization initiator A2: Compound formula (3) having a structure of the following formula (3)

Photopolymerization initiator Y1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (BASF Corporation "Irgacure 907")
Photopolymerization initiator Y2: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone ("IRGACURE 379" manufactured by BASF)
Photoinitiator Y3: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide ("Lucirin TPO" manufactured by BASF)
Photopolymerization initiator Y4: 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole ("Biimidazole" manufactured by Kurogane Kasei Co., Ltd.)
Photopolymerization initiator Y5: ethane-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
("Irgacure OXE02" manufactured by BASF)
Sensitizer E1:2,4-diethylthioxanthone ("Kayacure DETX-S" manufactured by Nippon Kayaku Co., Ltd.)
Sensitizer E2: 4,4′-bis(diethylamino)benzophenone (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.)

Photopolymerizable compound C: dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.)
Polyfunctional thiol F1: trimethylolpropane tri(3-mercaptobutyrate)
(Showa Denko's "TPMB")
Multifunctional thiol F2: pentaerythritol tetrakis (3-mercaptopropionate)
("PEMP" manufactured by Sakai Chemical Industry Co., Ltd.)

UV absorber G1: 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 , 3,5-triazine ("TINUVIN 400" manufactured by BASF)
Polymerization inhibitor H1: Methylhydroquinone (“MH” manufactured by Seiko Chemical Co., Ltd.)

Organic solvent: cyclohexanone

The obtained photosensitive coloring composition was evaluated by the following methods. The results are shown in Tables 4 and 5.
[Pattern formation of filter segment and black matrix]
The obtained photosensitive coloring composition was applied on a glass substrate of 10 cm×10 cm by spin coating, and then heated in a clean oven at 70° C. for 15 minutes to remove the solvent, and a coating film of about 2 μm was obtained. .. Then, after cooling this substrate to room temperature, it was exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Then, this substrate was spray-developed with an aqueous sodium carbonate solution at 23° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230° C. for 30 minutes. The spray development was carried out for the coating film of each photosensitive coloring composition in the shortest time capable of forming a pattern without development remaining, and this was defined as an appropriate development time.
The thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Sensitivity evaluation]
The pattern film thickness of the 100 μm photomask portion of the filter segment or the black matrix formed by the above method was measured, and the minimum exposure amount at which the film thickness after coating was 90% or more was evaluated. The smaller the minimum exposure amount, the more sensitive and good the photosensitive coloring composition becomes.
The evaluation ranks are as follows.
◎: less than ^{30mJ / cm 2 ○: 30mJ /} cm 2 or more 50mJ / cm less than ² △: 50mJ / cm ² or more 100mJ / cm ² less than ×: 100mJ / cm ² or more

[Linearity evaluation]
The pattern in the 100 μm photomask portion of the filter segment or black matrix formed by the above method was observed and evaluated using an optical microscope. The evaluation ranks are as follows.
○: Good linearity △: Partial poor linearity ×: Poor linearity

[Pattern shape evaluation]
The cross section of the pattern in the 100 μm photomask portion of the filter segment or the black matrix formed by the above method was observed and evaluated using an electron microscope. The pattern cross section has a good forward taper. The evaluation ranks are as follows.
◎: Forward tapered shape with gentle cross section ○: Forward tapered shape with cross section ×: Reverse tapered shape with cross section

[Resolution evaluation]
The pattern in the 25 μm photomask portion of the filter segment or the black matrix formed by the above method was observed and evaluated using an optical microscope. The evaluation ranks are as follows. Poor resolution means that adjacent stripe patterns are connected or chipped. The evaluation ranks are as follows.
⊚: Good resolution and linearity ◯: Slightly inferior in terms of linearity, but good resolution Δ: Poor linearity and partial chipping ×: Poor resolution

[Development resistance evaluation]
During spray development, the pattern film thickness was measured by measuring the pattern film thickness at the 100 μm photomask part of the filter segment or the black matrix formed by developing for twice the appropriate time, and developing at the appropriate development time. Compared with. The evaluation ranks are as follows.
◎: Film thickness difference within 20% ○: Film thickness difference greater than 20% and within 40%
X: The film thickness difference is larger than 40%. Or chipping or peeling occurs

[Chemical resistance evaluation]
The filter segment or the black matrix formed by the above method is immersed in an N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, air-dried, and evaluated by observing the pattern at the 100 μm photomask portion using an optical microscope. went. The evaluation ranks are as follows.
◎: Good appearance and color unchanged ○: Partially wrinkled, but good color unchanged ×: Peeling or discoloration

As shown in Tables 4 and 5, the filter segment and the black matrix formed using the photosensitive coloring compositions of Examples 1 to 19 have good sensitivity, linearity and resolution, and the photopolymerization of the present application. Examples 7 to 10, 12, 15, 16, and 18 in which the initiator (A) and the other photopolymerization initiator (Y) were used in combination showed more excellent characteristics due to the pattern shape. Among them, the other photopolymerization initiator (Y) is 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone. Examples 8, 12, and 16 were more excellent in sensitivity.

In addition, Examples 13 to 16 further containing a polyfunctional thiol (F) were excellent in sensitivity.
Further, Examples 3 and 5, which further contained the ultraviolet absorber (G) or the polymerization inhibitor (H), were excellent in resolution.
When other oxime ester-based photopolymerization initiators were used as in Comparative Examples 1 and 2, even if the sensitivity was good, the pattern shape was poor, and all of them were not good.
Further, in the case where the photopolymerizable compound (C) was not used as in Comparative Example 3, defective formation of the filter segment or the black matrix occurred, and no satisfactory one was obtained.

Claims (5)

Photosensitivity comprising a photopolymerization initiator (A) represented by the following general formula (1), a resin (B), a photopolymerizable compound (C), and a colorant (D). Coloring composition.
General formula (1)


[In the general formula (1), R ₁ is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted Or an unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted aryl It represents a sulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. At least one of R ₂ and R ₃ is an alkyl group substituted with a cycloalkyl group, and the other is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, A substituted or unsubstituted cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group is shown. ] The photosensitive coloring composition according to claim 1, further comprising another photopolymerization initiator (Y). The other photopolymerization initiator (Y) contains at least one compound selected from the group consisting of acetophenone compounds, phosphine compounds, and imidazole compounds, and the photosensitive coloring according to claim 2. Composition. The photosensitive coloring composition according to any one of claims 1 to 3, further comprising a polyfunctional thiol (F). A color filter comprising a filter segment or a black matrix formed of the photosensitive coloring composition according to claim 1 on a transparent substrate.